Palladium alloy

ABSTRACT

A family of alloys for use in medical, electrical contact and jewelry applications includes as primary components palladium, and boron and at least one of ruthenium, rhenium, platinum, gold, zirconium, tungsten, cobalt, nickel, tantalum and iridium. An alternative embodiment includes palladium and rhenium and/or ruthenium with an additional element iridium, platinum, tungsten, boron, gold, zirconium, cobalt, nickel and tantalum. The present alloy family has a high strength, high radio opacity, and biocompatibility characteristics, while also being workable into various configurations. Where required, some of the alloys also offer post form, heat treatment (age hardening) capabilities for even higher hardness and strength levels.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 60/569,671, filed May 10, 2004, which isincorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to a metal alloy, and inparticular, to an alloy including palladium, boron and one or moreadditional elements as solutes, and in particular to an alloy ofpalladium, boron and at least one of ruthenium, rhenium, iridium,platinum, tungsten, gold, zirconium, cobalt, nickel and tantalum. In analternative embodiment, the alloy is of palladium and at least one ofruthenium and rhenium with an additional element chosen from iridium,platinum, tungsten, boron, gold, zirconium, cobalt, nickel and tantalum.The invention also relates to a product formed of the foregoing alloys.

2. Description of the Related Art

Platinum alloys, in particular, platinum-iridium alloys have been usedin a wide variety of applications. Platinum-iridium alloys are widelyused for both disposable and implantable medical devices to fabricateradio opaque marker bands for catheters, electrode rings, platinum alloywires and coils, tubes, and machined components.

For example, radio opaque platinum-iridium alloys are used duringmedical procedures involving fluoroscope imaging since the radio opaqueplatinum-iridium alloy shows up very clearly in the fluoroscope image tothereby aid the medical personnel in performing their tasks.

The platinum-iridium alloy can also have a high yield strength orhardness along with well-established biocompatibility, which permits itto be used in implantable medical devices, such as pacemakers. The highyield strength also allows for the use of very fine wires that canaccept a high torque loading during the steering of catheters or guidewires through small diameter blood vessels. The higher strength wiresallow for a reduction in the wire diameter without a fear of breakageduring use. Smaller diameter wires allow for access into finer bloodvessels.

Platinum-iridium alloys are also popular for use in jewelrymanufacturing due to its excellent white color and good hardness as wellas its ability to be used in sheet stock, wire goods and investmentcasting. Platinum-iridium alloys have a higher melting temperature thangold alloys but can be investment cast or fabricated by cold working,hot working, and annealing, or soldering

Another application is in space vehicle applications, thermocouples,electrical contacts, etc.

Platinum-iridium alloys are sold in varying proportions of platinum toiridium. For example, the common proportions are 90% platinum to 10%,iridium, referred to as 90:10 alloy, an alloy of 85% Pt-15% Ir, or85:15, an alloy of 80% Pt to 20% Ir, or 80:20, an alloy of 75% Pt to 25%Ir, or 75:25, a 70:30 alloy, and even a 95:5 alloy.

In summary, platinum-iridium alloys are a mainstay in the medical marketand are used for everything from guide wire tips and coils, due to thegood radio opacity, to machined components and implantable pacemakercomponents. The jewelry trade uses the platinum-iridium alloys due totheir combination of strength and resistance to tarnish and oxidation.The platinum-iridium alloys provide a combination of strength andbiocompatibility.

However, the price of platinum has reached record levels, recentlyexceeding $900 per ounce, which is three times the current cost ofpalladium. This places significant economic strains on the continued useof high platinum alloys.

SUMMARY OF THE INVENTION

The present invention provides an alloy family sharing many of thecharacteristics of platinum-iridium alloys and is foreseeable as a lowercost replacement for platinum-iridium alloys. The present inventionprovides a family of alloys based on palladium and boron with anadditional component. The additional component is one or more of theelements chosen from the following; ruthenium, rhenium, iridium,platinum, tungsten, gold, zirconium, cobalt, nickel and tantalum. In afurther embodiment of the invention, the alloy is of palladium and oneor both of ruthenium and rhenium with an additional component chosenfrom the following: iridium, platinum, boron, tungsten, gold, zirconium,cobalt, nickel and tantalum. According to a further aspect, theinvention relates to a product formed of the foregoing alloys.

In a preferred embodiment, the additional component is one of rutheniumor rhenium or may be both ruthenium and rhenium. In one example of thepreferred embodiment, the palladium component is in a range of 45% to99.95%, the ruthenium component is in a range of 0% to 8%, the rheniumcomponent in the range of 0% to 25% (with the sum of the Ru and Recomponents generally exceeding 1%) and the boron component in a rangefrom 0.005% to 1.5%. Additional additives may be present in the alloy aswell.

In second preferred embodiment, the additional component may be one ormore of the following additives: platinum or gold in the range of Oto30%, rhenium in the range of Oto 25%, zirconium, tungsten, cobalt,nickel, tantalum or iridium in the range of 0 to 15%, ruthenium in therange of 0 to 8%, and boron in the range of 0.005 to 1.5% (with the sumof the boron plus all the other solutes generally exceeding 0.5%).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a radiograph showing radio opacity of alloys according to theprinciples of the present invention in comparison to stainless steel anda platinum iridium alloy at 50 KV;

FIG. 2 is a radiograph showing radio opacity of alloys according to theprinciples of the present invention in comparison to stainless steel anda platinum iridium alloy at 60 KV;

Table 1 is a table of palladium alloys assigned a sequence number andshowing constituents and characteristics;

Table 2 is a table of testing results for various alloys of the sequenceof Table 1 at various annealing temperatures;

Table 3 is a table of strip and wire characteristics of some alloys ofTable 1;

Table 4 is a table of strip test results for some alloys showing theeffect of boron on a palladium alloy with 4.5% ruthenium;

Table 5 is a table of strip test results for some alloys showing theeffect of cold work on the mechanical properties of selected alloys;

Table 6 is a table of radio opacity data for some alloys of Table 1along with text describing the test conditions

Table 7 is a table of three alloy compositions used in biocompatibilitytesting;

Table 8 is a table showing the results of biocompatibility testing for afirst of the alloys in Table 7;

Table 9 is a table showing the results of biocompatibility testing for asecond of the alloys in Table 7;

Table 10 is a table showing the results of biocompatibility testing fora third of the alloys in Table 7;

Tables 11A, 11B, and 11C, are tables showing put ups for various alloysin the present alloy family and the characteristics thereof;

Table 12 is a table showing the effect of boron on the age hardeningresponse for selected alloys.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In this document, the percentages of the alloy components refer toweight percent.

In the broadest sense, the present alloy is an alloy of palladium andboron with an additional element chosen from the following: ruthenium,rhenium, iridium, platinum, tungsten, gold, zirconium, cobalt, nickeland tantalum, or alternatively is an alloy of palladium and one or bothof rhenium and ruthenium with an additional element chosen from thefollowing: iridium, platinum, boron, tungsten, gold, zirconium, cobalt,nickel and tantalum. In one preferred embodiment, the alloy includespalladium and boron and at least one of ruthenium and rhenium. Anexemplary embodiment has proportions of palladium (Pd) in the range of45% to 99.95%, ruthenium (Ru) in the proportion of 0% to 8%, rhenium(Re) in the range of 0% to 25%, and boron (B) in the proportion of0.005% to 1.5%. The ruthenium and rhenium components can be both presentin the alloy, or the alloy may be formed with only one of theseelements. In addition, additives may be included as follows:

-   -   Platinum (Pt) up to 30%,    -   Gold (Au) up to 30%,    -   Zirconium (Zr) up to 15%,    -   Tungsten (W) up to 15%,    -   Cobalt (C) up to 15%,    -   Iridium (Ir) up to 15%,    -   Nickel (N) up to 15%, and    -   Tantalum (Ta) up to 15%.

Within this broad family of alloys are at least six differentsubcategories:

-   -   Pd—Ru—B, with or without additives;    -   Pd—Re—B, with or without additives;    -   Pd—Ru—Re—B, with or without additives;    -   Pd—B alloys, with one or more of the following additives Re, Ru,        Zr, Co, Ir, Ni, Ta, Au, Pt, and W.    -   Pd—Re alloys with one or more of the following additives B, Ru,        Zr, Co, Ir, Ni, Ta, Au, Pt, and W.    -   Pd—Ru alloys with one or more of the following additives B, Re,        Zr, Co, Ir, Ni, Ta, Au, Pt, and W.

The scope of this invention is not limited to the foregoing list ofadditives, but may include others.

The resulting alloys are capable of gaining additional strength due to aheat treating step, making use of an age hardening reaction.

The present alloys have a number of characteristics that make it aviable replacement for expensive platinum-iridium alloys, including ahigh degree of radio opacity (radiopaque), high strength, lower density,biocompatibility, and a lower cost. Each of these will be addressed inthe following. The present alloy is ideally suited as a medicalradiopaque marker, a medical lead, an implant component, electrodes, ora guidewire tips or coils. The alloy may be used in catheters, forexample as radiopaque markers, coils or feed-through components.

For use in the body, the alloy must be biocompatible. Three families ofalloys according to this disclosure, namely the Pd—Ru—B alloy, thePd—Re—B alloy, and the Pd—Ru—Re—B alloy, have all been tested forbiocompatibility and all three have passed a battery of five tests.Details of the biocompatibility tests are set forth in Tables 7, 8, 9and 10, as will be described in greater detail hereinafter.

The alloy families of the present invention provide a potential savingsof hundreds of dollars per ounce compared to commercial platinum-iridiumalloys. Thus, a first cost saving aspect is due to the lower costcomponents. The present alloys have a lower density level than theplatinum-iridium alloys so that each ounce of material provides a largervolume of material while still providing a strength generally equivalentto, and in some cases exceeding that, of 90% platinum-10% iridiumalloys. The lower density is a second cost saving aspect. The type andproportion of added elements can vary the density of the alloy. However,density levels for the alloys within the scope of this invention offerdensities that are 20% to 50% lower than a 90% platinum-10% iridiumalloy.

The high strength palladium-boron plus additive alloys envisioned bythis invention provide improved mechanical properties and processingcharacteristics verses conventional palladium-ruthenium casting alloysused in some jewelry alloys. The strength of the material is importantfor many applications, particularly for in-body applications. Thepresent alloy has excellent strength characteristics. The mechanicalproperties are reported in tables described hereinbelow.

Various alloys in the present alloy family have been prepared andtested. In the processing of these alloys, alternating steps of coldworking, typically followed by an annealing step, is performed. At theend of the processing sequence, the cold working is often followed by astress relief annealing step for improved ductility. The resulting alloyhas a high strength in combination with good formability. The coldworking has been performed with a 50% cold working, and with 75% coldworking which yields an even harder alloy. For example, the hardness ofan embodiment of the alloy before and after cold working by 75% changedfrom 134 to 270 Knoop. A similar change is seen in a further embodimentof 265-400 Knoop. The processing and resulting characteristics isreported in the accompanying tables.

In general, a four element alloy version (Pd—Ru—Re—B) of the presentinvention provides the same strength level as the 90-10 platinum-iridiumalloy at half the total solute content. As noted herein, three elementalloy versions (also referred to a ternary alloys) (Pd—Ru—B or Pd—Re—B)also provide excellent replacement possibility for the platinum-iridiumalloys. The present alloy system provides high strength levels without aloss of processability.

In particular applicants have found, surprisingly, that synergies existwhen boron is added to the ruthenium and/or rhenium containing alloys.For example, while alloys 933 and 938 as shown in Table 11 A differ byonly about 0.35% boron, the addition of boron resulted in a doubling ofcold worked hardness while maintaining surprising ductility. Similarincreases in cold hardness is seen for many of the paired alloys showedin Tables 11A, 11B and 11C.

For example, applicants have discovered boron shows the same markedsynergy when rhenium is present without ruthenium. Comparison of alloys897 and 893 demonstrate this synergy. The addition of only about 0.35%boron to a 10% rhenium containing alloy caused an increase in coldworked hardness from Knoop 319 without the boron to Knoop 477 with boronadded.

An increase in solute levels of Re in the alloy to about 11% hasprovided very strong alloys.

Applicants have also found, and disclosed in the tables, and inparticular in Tables 1-11, that the proportions of ruthenium, rheniumand boron in these alloys can be varied such that alloys having moreboron require less ruthenium and/or rhenium to reach the same hardnesslevels.

As noted herein, applicants have further discovered that additions ofother elements further add to the remarkably high strength and ductilityof these alloy families. By way of demonstrating these effects, whenapplicants added 10% of tungsten to Alloy 917, thereby creating alloy981 applicants increased the cold worked hardness from Knoop 423 toKnoop 503, without sacrificing ductility. Having ductility at such highhardnesses has not, as far as applicants know, been reported for otheralloys containing either platinum or palladium as their majorconstituents. By ductility in the foregoing examples, applicants referto the condition of the edge of the strip samples as they are rolled, orwrought, down to thinner thicknesses such that the high hardnessachieved by cold working was not accompanied by edge defects as thoseskilled in the art would expect to find while trying to cold work alloysof such high hardnesses.

To put the above increases of hardness into clearer perspective, testsdone on the binary combinations of these elements do not reach theseextreme hardness values. For example, alloy 925, consisting of palladiumplus 0.35% boron added had a cold worked hardness of only Knoop 270 at75% CW. Similarly an alloy, alloy 935, consisting of palladium plus 4.0%ruthenium had a cold worked hardness only Knoop 208 at 75% CW level.Likewise an alloy consisting of palladium plus 5% rhenium, alloy 887,had a cold worked hardness of only Knoop 265 with 75% CW.

The attached tables include a Table 1 showing alloys numbers 844 through884, and identify the constituent components as well as the percentageof elongation and hardness results from testing at 50% cold work. Boroncontent in these specifications refers to the proportion of boron addedduring initial alloying, not to the proportion of boron found in thefinished alloy. Due to the poor efficiency of capturing boron additionsin the molten metal, a retention of only about 20% to 60% of thequantity originally added during alloying is found.

Table 2, identified as short term thermal tests, shows short term heattreatment tests for alloys No.880, 882, and 883, each of which have beencold worked to two different percentages of cold work. The results ofthe hardness testing are shown both before and after the heat treatment.For all three alloys the hardness increase with thermal exposure showinginitial evidence of an age hardening response. The response in morepronounced with increased cold work prior to aging.

Table 3 illustrates the properties of the alloy 852 that has been formedinto a strip and into a wire, contrasting the strip verses wireproperties, including the benefits of a stress relief anneal to providea significant increase in elongation.

Table 4 presents the test results for alloys 846 and 851-853illustrating the effect of increased boron in a Pd-4.5% Ru alloy.

Table 5 presents test results for alloys 877 to 886, and illustrates thesignificant increase in mechanical properties for cold work factors over50%.

Table 6 describes the radiopacity trials done on selective alloysaccording to the invention. The testing reveals a high degree ofradiopacity for the embodiments of the invention. The test conditionsare as follows. X-ray testing was done at radiographic laboratory (usingstandard equipment). All the metal samples were 0.009 inches thick. Theinitial (50 KV) tests used conventional settings for extremity cassetteexposure. Exposures were also done at increased X-ray tube voltages.This acts to increase the penetrating power of the x-ray and makes itharder to detect the stainless steel sample. However, both the 90Pt-10Irsample and alloys 847, 879 and 883 according to this invention were easyto see over all test conditions used. The stainless steel and 90Pt-10IRcoupons are included as comparison standards.

A key characteristic of the platinum-iridium alloys which should befound in a viable replacement is that of radio opacity. Since radioopacity tends to follow density, the densities of the present alloyshave good radio opacity for most applications. In particular, thepresent alloy is denser than stainless steel and thus will be more radioopaque than stainless.

A common belief is that the radiopacity of material is a cubic functionof the atomic number. The atomic number of platinum is 78 and the atomicnumber of palladium is 47, yet the tests have revealed a surprisingresult in that the present alloys are nearly as radio opaque as theplatinum-iridium alloys. The Table 6 and following figures demonstratethe radiopacity of these alloys compared to 17-4 PH stainless steel and90% platinum-10% iridium.

FIGS. 1 and 2 show two of the actual radiographs described in Table 6.The samples of the present alloy have one, two or three corners cut offand the comparison sample of stainless steel has four corners cut off,while a comparison sample of Pd-Ir has no corners cut off. In FIG. 1,the test has done with samples of the alloys 847, 879 and 883 and withstainless steel and a 90:10 platinum-iridium alloy for comparison. Thesamples were all prepared to a thickness of 0.009 inches in thicknessand were x-rayed in a standard x-ray machine of with the x-ray tubevoltage set at 50 Kv. The stainless steel sample has a low radiopacityby comparison, whereas the platinum-iridium sample has a highradiopacity. The alloys of the present invention also have a highradiopacity, approaching that of the platinum-iridium sample.

In FIG. 2, the tube voltage was increased to 60 Kv to increase thepenetration of the x-rays. The stainless steel sample nearly disappearsbut the present alloys, 847, 879 and 883, and the platinum-iridiumsample have a high degree of radiopacity. In the view of FIG. 2, thebackground has been lightened to show the location of the stainlesssteel sample, which would otherwise not be apparent.

Densitometer measurements of the film was done after exposure to thex-rays at various tube voltages. At 50 Kv, the stainless steel has arating of 0.66, the three alloys 847, 879 and 883 each have ratings of0.20, and the Pd-Ir alloy has a rating of 0.20. At a tube current of 60Kv, the stainless steel sample rating is 2.17, the three alloys samples847, 879 and 883 are rated at 0.25, 0.23 and 0.24, respectively, and theP1-Ir sample is 0.22. A further increase of the tube current to 70 Kvresults in a measured rating for the stainless steel sample at 3.28, forthe three alloys 847, 879 and 883 at 0.72, 0.62 and 0.66, respectively,and for the Pd—Ir sample at 0.39.

Uses of the present alloy family include in medical devices includingradio opaque medical devices, machined medical devices and implantablemedical devices. In addition, the present alloy may readily be used inelectrical contact applications, the jewelry market and otherapplications requiring high strength, high hardness and good tarnishresistance. The present alloys are particularly advantageous as lownoise signal contacts and may be used as either sliding electricalcontacts or static electrical contacts.

The present alloy is seen as a replacement for 90:10 platinum-iridiumalloys as well as 85:15 platinum-iridium alloys and may replace 80:20platinum-iridium alloys in some applications. Mechanical testing hasbeen carried out on the alloys of this alloy family and the results areset forth in the tables. The strength data included testing of the rawalloys, testing after cold working in various percentages and afterannealing for stress relief at various temperatures. For example, coldworking has been carried out at 50% and at 75%, with a higher strengthproduct seen after the 75% cold working.

The thermal exposure data in Tables 2 and 12 indicate that for some ofthe alloys within this family, higher strength and hardness levels areachievable though the use of a post form heat treatment.

Particularly high strength and hardness values are seen, for example, inalloys 880, 882, and 883 wherein the strength, measured in the Knoophardness scale increases significantly after stress relief annealing. Inparticular, see alloy No. 883. Referring to the table of alloys in thealloy family, alloy No. 883 has proportions of palladium of 90.15%,ruthenium of 4.5%, and boron of 0.35% and 5% rhenium. The percentage ofrhenium may extend up to 20%, as may be determined by reference to apalladium rhenium binary phase diagram. The alloy No. 883 reached aKnoop hardness level of 503, after a short term aging anneal following66% cold work, thus holding particular promise. This increasing hardnesswhen held at an intermediate temperature suggests that some of thealloys in this family undergo an age hardening or ordering reaction.This is further illustrated in Table 12.

Thus, the strength of the present alloy families has been shown. Thepresent alloy family has proven to be biocompatible as well. In general,members of the platinum group metals are biocompatible. Although rheniumis a refractory metal, it shares many of the physical, chemical, andmechanical characteristics of the platinum group elements, and thiselement is known to have good biocompatibility and osteoconductivitycharacteristics.

In Table 7 is a listing of alloys 847, 900 and 902, the components ofwhich are shown in the table, that have been formed into strips andwires and tested for biocompatibility. The three alloys passed fivebiocompatibility tests, including: 1) cytotoxicity using the ISO elutionmethod, 2) ISO intracutaneous testing using aqueous and organicextraction, 3) ISO systemic toxicity testing using aqueous and organicextraction, 4) ISO muscle implant for two weeks, and 5) in vitrohemolysis using aqueous extraction (a modified ASTM process).ASTM=American Society for Testing and Materials.

Tables 8, 9 and 10 show the specific testing results for each of thealloys 847, 900 and 902, respectively, in the form of a test matrix. Theresults show excellent biocompatibility for these materials.

Testing as to formability of the present alloy family suggests that theymay be formed into spring coils and the like without cracking, which issurprising for materials of such high hardness.

Tables 11A, 11 B, and 11C show examples of alloys, including alloys 924through 1014. In most cases, the alloys are paired together to show theincreased mechanical properties that occur with small additions ofboron. The alloy put up compositions are shown as is information onhardness, tensile strength and processability. In some cases, the alloyswork hardened to such a degree that additional reductions exceeded thehold down force of the rolling mill. These cases are shown with circlesaround the resultant cold work percentage.

Table 12 shows the age hardening response of the alloys 948, 952, 953and 954 which shows the hardness results for three boron containingalloys with higher solute levels. All of these alloys achieved hardnesslevels above 500 Hk(100) after aging. As in cold work cases shown inTables 11A-C, the addition of the B (boron) greatly enhanced the finalhardness.

The data presented in the tables also reveals that alloys of palladiumwith rhenium and an additional component and alloys of palladium withruthenium and an additional component have a characteristics which makethem a viable and valuable replacement for the platinum-iridium alloysof the prior art. In particular, such palladium and either rhenium orruthenium based alloys with an additional component have tested to ahigh strength. These palladium and either ruthenium or rhenium basedalloys are presented as alloy numbers 994, 980, 971 and 957 in thetables. Testing of these alloys has revealed a shortcoming for theseembodiment, in that there is a lack of ductility. However, the reducedductility characteristic is less important in casting alloys and so itis foreseen that these alloys may be used in cast products. It is alsoforeseeable that further anneals for processing these alloys mayincrease the ductility characteristic, although testing of such furtherprocessing has not yet been completed.

Thus, there is disclosed an alloy which is a viable replacement toplatinum iridium alloys while providing a lower cost and meeting thesignificant characteristics of the more expensive known alloy. Thepresent alloy family includes alloys with varying ranges of componentsand various additives as noted above. These alloys may be used inmedical applications, where they are worked and annealed and may beformed into strips or wires, or tubes, or coils, or into machinedcomponents. In addition, it is foreseen that the present alloy familymay find applications as sliding electrical contact materials (wherehigh hardness and tarnish resistance is required), utility in castjewelry (rather than worked metal), or may be utilized in various otherapplication where the advantageous characteristics of this alloy familyare required.

The examples presented hereinbelow represent the current optimization ofembodiments. However, further changes, additions or deletions may alsobe possible and are within the scope of this invention.

EXAMPLES OF PREFERED EMBODIMENTS

Within the broad families of alloys that are within the scope of thisinvention are a number of more preferred compositions that are ideallysuited to particular applications. For instance, a preferred alloy of afirst embodiment has a balance of Pd (palladium)—about 10.5% Re(rhenium)—and about 0.08% B (boron) nominal. The ranges of thecomponents for this first embodiment are: Re (rhenium) 10.5% plus orminus 0.5%—B (boron) 0.08% plus or minus+0.05%—and a balance of Pd(palladium). This embodiment has attributes of low cost, low density,biocompatible (similar to PE 902), good radiopacity, and high strength.The potential uses for this alloy include use as catheter coils; trailsindicate coiling characteristics similar to Pt—Ni and Pt—W alloys.

An alloy according to the first embodiment, which is referred to in thetables as alloy 100, has been formed into wires with diameters between0.0025 inch and 0.010 inch. The alloy is provided in two grades, astandard grade and a medical grade. The standard grade has a balance ofPd, 10 to 11% Re, 0.03 to 0.13 B, a maximum of 1000 ppm for each of Rh,Pt, Ru, Os, Au and Ag, and a maximum of 0.2% of other ingredients. Themedical grade has a balance of Pd, 10 to 11% Re, 0.03 to 0.13 B, amaximum of 1000 ppm for each of Rh, Pt, Ru, Os, Au and Ag, a total of 30ppm maxium for Pb, As, Bi and Cd, a maximum 100 ppm for Cu, a maximum 75ppm for Ni, a maximum 100 ppm for Fe, and a maximum 500 ppm for otheringredients excluding Rh, Pt, Ru, Os, Ag and Au, with a maximum 200 ppmfor all other elements. For a wire according to this embodiment of adiameter of 0.002 inches to 0.015 inches, a stress relieved strength(UTS) of 180 to 235 ksi has been achieved for an elongation of 2.5%minimum in 10 in gauge length.

In this first embodiment, the primary solutes are Pd, Re and B. Thecomponent Ru can be treated as a potential additive

In a second embodiment, the alloy has a balance of Pd—about 5% Re—andabout 0.08% B nominal. The ranges for the components are Re 5% plus orminus 0.5%—B 0.08% plus or minus 0.05% and a balance of Pd. Thisembodiment has attributes of low cost, low density, biocompatible, goodradiopacity, and moderate strength.

In a third embodiment, the alloy has a balance of Pd—about 10% W—about4% Ru—and about 0.08% B nominal. The components of this embodiment arein a range of W 10% plus or minus 0.5%—Ru 4% plus or minus 0.5%—B 0.08%plus or minus 0.05% and a balance of Pd. The attributes of thisembodiment are low cost, low density, very high hardness with goodprocessability, good radiopacity, and high strength.

In a fourth embodiment, the alloy has a balance of Pd—about 20% Re—about4% Ru—and about 0.08% B nominal. The components of this embodiment arein a range of Re 20% plus or minus 1%—Ru 4% plus or minus 0.5%—B 0.08%plus or minus 0.05% and a balance of Pd. The attributes of this alloyare low cost, low density, good radiopacity, high strength, and an agehardenable system capable of reaching hardness level of nearly 600 Hk.

In a fifth embodiment, the alloy has a balance of Pd—about 2% Ru—andabout 0.08% B nominal. The ranges are Ru 2% plus or minus 0.5%—B 0.08%plus or minus 0.05% and a balance of Pd. The attributes are low cost,low density, good radiopacity, and moderate strength.

The benefits of all these alloys—low density with unexpected highstrength and high radiopacity. Also much lower cost that Pt alloys—twofold benefit—lower intrinsic value for Pd verses Pt (currently a factorof nearly 4 to 1), and lower density gives additional benefit of morematerial per oz. Radiopacity is unexpected since at Kev (x-ray energylevel) of interest here—we were told radiopacity should be a cubicfunction of the atomic number (Pd is 47 and Pt is 78), and yet as shownin the provisional patent application these alloys are very close toPt—Ir alloys.

Although other modifications and changes may be suggested by thoseskilled in the art, it is the intention of the inventors to embodywithin the patent warranted hereon all changes and modifications asreasonably and properly come within the scope of their contribution tothe art. TABLE 1 Selected Alloys Evaluated put up at 50% CW Severe alloy# Pd Ru B Ir Re Pt W Au Zr Co UTS % el hard Edge cracking 844 99.65 0.3567 0.2 176 no 845 98.15 1.5 0.35 89 1.1 222 no 846 95.5 4.5 108 0.6 248no 849 95.45 4.5 0.05 121 0.8 303 no 850 95.43 4.5 0.075 107 0.6 267 no851 95.4 4.5 0.1 107 0.7 280 no 852 95.3 4.5 0.2 123 0.7 309 no 825 95.24.5 0.3 108 0.3 no 847 95.15 4.5 0.35 114 1.3 286 no 826 95.05 4.5 0.150.3 137 0.8 no 853 94.8 4.5 0.7 143 1.1 389 yes 822 94.5 5.5 104 0.9 yes854 94.5 4.5 1 126 0.1 308 yes 858 94.15 4.5 0.35 1 127 1 291 no 86394.15 4.5 0.35 1 109 0.2 291 no 864 94.15 4.5 0.35 1 121 0.6 292 no 85594 4.5 1.5 114 0.1 435 yes 848 93.15 6.5 0.35 118 1.1 292 yes 827 93.054.5 0.15 0.3 2 122 0.8 no 812 92.5 7.5 no 820 92.5 4.5 3 131 0.5 no 85992.15 4.5 0.35 3 128 0.7 311 yes 856 91.65 8 0.35 286 yes 821 91.5 5.5 3yes 811 90.5 4.5 0.5 4.5 106 0.5 243 yes 857 89.65 10 0.35 >482 yes 86085.15 4.5 0.35 10 122 0.4 303 no 861 85.15 4.5 0.35 9.2 0.8 135 1.1 328no 862 85.15 4.5 0.35 10 111 1 266 no

TABLE 2 Short Term Thermal Tests Hardness, HK(100) vs. AnnealTemperature As Cold Annealing Temperature, ° C. for 1 minute PE # % CWWorked 450 500 550 600 700 750 880 50 338 365 348 345 371 360 343 67 333465 451 443 451 419 429 882 50 325 368 378 384 377 368 350 69 439 491472 457 465 453 444 883 50 367 414 404 415 418 338 395 66 449 503 476462 461 459 461 Alloy Composition Pd Pt Ru B Re W 880 79.85 15 4.5 .35.3 882 79.85 13.8 4.5 .35 .3 1.2 883 90.15 4.5 .35 5

TABLE 3 Strip vs. Wire Properties as Cold Worked And The BeneficialEffect Of A Stress Relief Anneal on Elongation of Cold Worked Wire 0.2%Elonga- Alloy Condition UTS YS tion (Composition) (Size) (ksi) (ksi) (%)PE-852 Strip 50% CW (.009″) 122.6 117.7 <1 (95.3 Pd, 4.5 Ru, 0.2 B)PE-852-2 Wire 48% CW (.095″) 149.0 — <1 (95.3 Pd, 4.5 40% CW + SR 134.5— 8.8 Ru, 0.2 B) (.102″)

TABLE 4 Effect of B in a Pd - 4.5% Ru Alloy Alloy UTS 0.2% YS ElongationHardness Edge (Composition) Condition (Size) (ksi) (ksi) (% in 2″)(HK100) Condition PE-846 50% CW (.009″) 107.5 104.3 0.6 248 1 (95.5 Pd,4.5 Ru) PE-851 50% CW (.009″) 106.6 102.4 0.7 280 1 (95.4 Pd, 4.5 Ru,0.1 B) PE-852 50% CW (.009″) 122.6 117.7 0.7 309 1 (95.3 Pd, 4.5 Ru, 0.2B) PE-853 50% CW (.009″) 142.7 133.1 1.1 389 4 (94.8 Pd, 4.5 Ru, 0.7 B)

TABLE 5 Strip Test Results Showing Some Effects of Cold Work on VariousAlloys Alloy UTS 0.2% YS Elongation Hardness Edge (Composition)Condition (Size) (ksi) (ksi) (% in 2″) HK100 Condition PE-877 50% CW(.009″) 127.8 94.0 0.2 264 1 (96.35 Pd, 3.0 Ru, .35 B, 0.3 Re) 75% CW(.008″) 177.5 141.3 0.8 380 1 PE-879 50% CW (.009″) 134.1 132.7 0.1 3371 (80.15 Pd, 15.0 Pt, 4.5 Ru, 0.35 B) 69% CW (.0103″) 172.6 152.8 1.0456 1 PE-880 50% CW (.009″) 140.6 136.9 0.8 338 1 (79.85 Pd, 15.0 Pt,4.5 Ru, .35 B,.3 Re) 67% CW (.0108″) 182.0 163.6 0.8 333 1 PE-881 50% CW(.009″) 150.0 149.4 0.1 334 1 (80.15 Pd, 13.8 Pt, 4.5 Ru, .35 6,1.2 W)66% CW (.0113″) 192.7 169.7 0.9 433 1 PE-882 50% CW (.009″) 140.9 137.60.1 325 1 (79.85 Pd, 13.8 Pt, 4.5 Ru, .3 Re, 69% CW (.0102″) 191.1 164.91.2 439 1 0.35 B, 1.2W) PE-883 50% CW (.009″) 161.0 153.2 0.1 367 1(90.15 Pd, 4.5 Ru, 5.0 Re, 0.35 B) 66% CW (.0113″) 186.2 168.4 0.5 449 1PE-884 50% CW (.009″) 149.0 146.4 0.7 395 4 (70.15 Pd, 4.5 Ru, 25.0 Pt,0.35 B) 68% CW (.0106″) 203.0 — 0.1 487 4 PE-885 50% CW (.009″) 121.7116.1 0.6 334 4 (83.65 Pd, 6.0 Ru, 10.0 Pt, 0.35 B,) 68% CW (.0106″)167.1 144.8 0.5 445 4 PE-886 59% CW (.00725″) 140.2 — 0.1 370 4 (81.15Pd, 6.0 Ru, 0.35 6, 10.0 Pt, 69% CW (.0102″) — — — 507 4 2.5 Re)

TABLE 6 Radiopacity Data Summary of test conditions: X-ray testing wasdone at local radiographic laboratory (using standard equipment). Allthe metal samples were .009″ thick. The initial (50 KV) tests usedconventional settings for extremity cassette exposure. Exposures werealso done at increased X-ray tube voltages. This acts to increase thepenetrating power of the x-ray and makes it harder to detect thestainless steel sample. However, both the 90Pt-10lr sample and alloyswithin the scope of this invention were easy to see over all testconditions used. The stainless steel and 90Pt-10lr coupons are includedas comparison standards. Summary of Radiographic Data (densitometerreadings) Alloy 50 Kv 60 Kv 70 Kv 17-4 PH .66 2.17 3.28 Stainless steelAlloy 847 .20 .25 .72 Alloy 879 .20 .23 .62 Alloy 883 .20 .24 .6690Pt-10lr .20 .22 .39

TABLE 7 Materials used for Biocompatibility Testing AnalyzedCompositions (wt %) Alloy Pd Re Ru B Au Zr Fe Pt Ir PE-847 strip 95.70 —4.19 0.05 0.01 0.03 0.03 wire 95.74 4.17 0.04 0.02 0.03 PE-900 strip89.04 9.20 1.67 0.03 0.01 0.17 wire 89.03 4.70 0.04 0.14 PE-902 strip89.27 10.51 — 0.03 0.19 0.01 wire 89.66 10.12 0.03 0.19

TABLE 8 Biocompatibility Test Results for alloy 847 Test Method andCriteria Results Cytotoxicity - MEM elution with L929 mouse Noreactivity ISO 10993-5 fibroblast cell culture Irritation andIntracutaneous injection with Irritation Sensitization aqueous andorganic extracts judged as ISO 10093-10 slight to negligible SystemicToxicity- Systemic injection with aqueous No adverse ISO 10993-11 andorganic extracts biological reaction Interactions Hemolysis study byextract 0.0% with Blood hemolysis ISO-10993-4 Implantation 2 weekimplant in muscle of rabbit No adverse ISO-10993-6 biological reactions

TABLE 9 Biocompatibility Test Results for alloy 900 Test Method andCriteria Results Cytotoxicity - MEM elution with L929 mouse Noreactivity ISO 10993-5 fibroblast cell culture Irritation andIntracutaneous injection with Irritation Sensitization aqueous andorganic extracts judged as ISO 10093-10 negligible Systemic Toxicity-Systemic injection with aqueous No adverse ISO 10993-11 and organicextracts biological reaction Interactions Hemolysis study by extract0.0% with Blood hemolysis ISO-10993-4 Implantation 2 week implant inmuscle of rabbit No adverse ISO-10993-6 biological reactions

TABLE 10 Biocompatibility Test Results for alloy 902 Test Method andCriteria Results Cytotoxicity - MEM elution with L929 mouse Noreactivity ISO 10993-5 fibroblast cell culture Irritation andIntracutaneous injection with Irritation Sensitization aqueous andorganic extracts judged as ISO 10093-10 slight to negligible SystemicToxicity- Systemic injection with aqueous No adverse ISO 10993-11 andorganic extracts biological reaction Interactions Hemolysis study byextract 0.0% with Blood hemolysis ISO-10993-4 Implantation 2 weekimplant in muscle of rabbit No adverse ISO-10993-6 biological reactions

TABLE 11 A Hardness Hard. change Put-Up Composition, wt % Edge* HK withB UTS Alloy Code Pd Re Ru B Pt Ir W Au Zr Co Ni % CW Cond. (100)addition ksi PE 924 100.00 75 1 134 51 PE 925 99.65 0.35 75 1 270 136 98PE 887 95.00 5.00 75 1 265 105 PE- 889 94.65 5.00 0.35 75 1 398 133 146PE- 897 90.00 10.00 75 2 319 137 PE- 893 89.65 10.00 0.35 75 1 477 158191 PE- 899 85.00 15.00 75 3 391 150 PE- 891 84.65 15.00 0.35

3 537 146 230 PE- 928 80.00 20.00

4 452 191 PE 930 79.65 20.00 0.35

4 585 133 PE 932 99.50 0.50 75 1 159 60 PE 937 99.15 0.50 0.35 75 1 284125 102 PE- 933 99.00 1.00 75 1 166 65 PE- 938 98.65 1.00 0.35 75 1 328162 124 PE- 934 98.00 2.00 75 1 178 69 PE- 939 97.65 2.00 0.35 75 1 369191 136 PE- 935 96.00 4.00 75 1 208 85 PE- 917 95.65 4.00 0.35 75 2 423215 170 PE- 936 92.00 8.00 75 4 318 141 PE 856 91.65 8.00 0.35 75 4 495177 193 PE 941 89.00 10.00 1.00 75 1 329 141 PE 950 88.65 10.00 1.000.35

2 463 134 208 PE 942 83.00 15.00 2.00 75 3 398 185 PE 952 82.65 15.002.00 0.35

4 362 na

Note-Work Hardening level too high to allow continued processing withoutintermediate anneal

TABLE 11 B Hardness Hard. change Put-Up Composition, wt % Edge* HK withB UTS Alloy Code Pd Re Ru B Pt Ir W Au Zr Co Ni % CW Cond. (100)addition ksi PE- 957 80.00 10.00 10.00 75 2 402 176 PE- 958 79.65 10.000.35 10.00 75 3 485 83 192 PE- 959 86.00 4.00 10.00 75 3 393 174 PE- 96085.65 4.00 0.35 10.00 75 4 458 65 PE- 961 76.00 10.00 4.00 10.00

4 430 PE- 962 75.65 10.00 4.00 0.35 10.00 75 4 452 22 198 PE- 964 80.0010.00 10.00 75 1 347 149 PE- 965 79.65 10.00 0.35 10.00 75 4 503 156 214PE- 966 86.00 4.00 10.00 75 2 266 107 PE- 967 85.65 4.00 0.35 10.00 75 1385 119 169 PE- 968 76.00 10.00 4.00 10.00 75 4 391 173 PE- 969 75.6510.00 4.00 0.35 10.00

4 586 195 PE- 971 80.00 10.00 10.00

2 516 219 PE- 972 79.65 10.00 0.35 10.00 75 4 552 36 181 PE- 973 86.004.00 10.00 75 4 468 161 PE- 974 85.65 4.00 0.35 10.00

4 525 57 192 PE- 975 76.00 10.00 4.00 10.00

4 479 PE- 976 75.65 10.00 4.00 0.35 10.00

4 481 2 PE- 978 80.00 10.00 10.00 75 4 440 132 PE- 979 79.65 10.00 0.3510.00

4 566 126 234 PE- 980 86.00 4.00 10.00 75 2 350 154 PE- 981 85.65 4.000.35 10.00

1 503 153 218 PE- 982 76.00 10.00 4.00 10.00

4 457 PE- 983 75.65 10.00 4.00 0.35 10.00

4 546 89

Note-Work Hardening level too high to allow continued processing withoutintermediate anneal

TABLE 11 C Hardness Hard. change Put-Up Composition, wt % Edge* HK withB UTS Alloy Code Pd Re Ru B Pt Ir W Au Zr Co Ni % CW Cond. (100)addition ksi PE- 985 80.00 10.00 10.00 75 1 367 165 PE- 986 79.65 10.000.35 10.00 75 1 426 59 178 PE- 987 86.00 4.00 10.00 75 3 346 166 PE- 98885.65 4.00 0.35 10.00

2 413 67 186 PE- 989 76.00 10.00 4.00 10.00 75 4 406 172 PE- 990 75.6510.00 4.00 0.35 10.00 75 4 485 79 188 PE- 992 80.00 10.00 10.00

4 414 PE- 993 79.65 10.00 0.35 10.00

4 488 74 PE- 994 86.00 4.00 10.00 75 1 347 151 PE- 995 85.65 4.00 0.3510.00 75 4 473 126 153 PE- 996 76.00 10.00 4.00 10.00

4 388 PE- 997 75.65 10.00 4.00 0.35 10.00

4 462 74 PE- 999 80.00 10.00 10.00 75 1 315 139 PE- 1000 79.65 10.000.35 10.00

1 460 145 192 PE- 1001 86.00 4.00 10.00 75 1 233 105 PE- 1002 85.65 4.000.35 10.00 75 1 360 127 138 PE- 1003 76.00 10.00 4.00 10.00

4 449 PE- 1004 75.65 10.00 4.00 0.35 10.00

4 507 58 PE- 955 90.00 10.00 75 1 281 119 PE- 956 89.65 0.35 10.00 75 1357 76 132 PE- 970 90.00 10.00 75 1 459 180 PE- 1010 89.65 0.35 10.00 754 486 27 132 PE- 977 90.00 10.00 75 1 301 126 PE- 1011 89.65 0.35 10.0075 1 471 170 192 PE- 984 90.00 10.00 75 1 274 114 PE- 1012 89.65 0.3510.00 75 1 380 106 150 PE- 991 90.00 10.00 75 1 250 97 PE- 1013 89.650.35 10.00 75 1 360 110 171 PE- 998 90.00 10.00 75 1 162 66 PE- 101489.65 0.35 10.00 75 1 288 126 108 PE- 963 90.00 10.00 75 1 178 69 PE-1009 89.65 0.35 10.00 75 1 336 158 140

Note-Work Hardening level too high to allow continued processing withoutintermediate anneal

TABLE 12 Increased Age Hardening Response when adding B to Pd—Ru—Realloys Hardness Hardness Hk(100) increase As After Hardness from AlloyComposition (wt %) cold 760 F./60 m increase adding B Alloy code Pd ReRu B % CW worked HT after HT (after HT) PE- 942 83.00 15.00 2.00 50 398453 26 134 PE- 952 82.65 15.00 2.00 0.35 50 362 522 160 PE- 943 76.0020.00 4.00 AC 481 487 6 117 PE- 953 75.65 20.00 4.00 0.35 50 468 591 123PE- 942 67.00 25.00 8.00 AC 398 453 26 37 PE- 954 66.65 25.00 8.00 0.3545 486 549 63

1. An alloy for in-body medical use, comprising: an alloy of palladiumand boron and a third element, said alloy being formed into a device forin-body medical use.
 2. An alloy as claimed in claim 1, wherein saidthird element is at least one of rhenium, ruthenium, iridium, platinum,tungsten, gold, zirconium, cobalt, nickel and tantalum.
 3. An alloy asclaimed in claim 1, wherein said alloy has a structure corresponding tohaving been cold worked and stress relief annealed.
 4. An alloy asclaimed in claim 1, wherein said alloy has a structure corresponding tohaving been heat treated after forming.
 5. An alloy as claimed in claim3, wherein said structure of said alloy corresponds to having been coldworked up to 50 percent.
 6. An alloy as claimed in claim 3, wherein saidstructure of said alloy corresponds to having been cold worked up to 75percent.
 7. An alloy as claimed in claim 3, wherein said structure ofsaid alloy corresponds to having been cold worked beyond 75 percent. 8.A product formed of an alloy, comprising: an alloy of palladium andboron and a third element, said third element is at least one ofrhenium, ruthenium, iridium, platinum, tungsten, gold, zirconium,cobalt, nickel and tantalum.
 9. A product as claimed in claim 8, whereinsaid product is an in-body medical device.
 10. A product as claimed inclaim 8, wherein said product is an electrical contact.
 11. A product asclaimed in claim 10, wherein said electrical contact is a low noisesignal sliding contact.
 12. A product as claimed in claim 10, whereinsaid electrical contact is a low noise signal static contact.
 13. Analloy for in-body medical use, comprising: an alloy of palladium,rhenium and boron, said alloy having palladium in a range of 45 to 99.95percent, boron in a range of 0.005 to 1.5 percent, and rhenium in arange of 0 to 25 percent.
 14. An alloy as claimed in claim 13, whereinsaid alloy further includes ruthenium in a range of 0 to 8 percent. 15.An alloy comprising three primary elements as follows: a first primaryelement Pd as a balance of the alloy; a second primary element Re in arange of 10.5%±0.5%; and a third primary element B in a range of0.08%±0.05%.
 16. An alloy comprising three primary elements as follows:a first primary element Pd as a balance of the alloy; a second primaryelement Re in a range of 5%±0.5%; and a third primary element B in arange of 0.08%±0.05%.
 17. An alloy comprising four primary elements asfollows: a first primary element Pd as a balance of the alloy; a secondprimary element Ru in a range of 4%±0.5%; a third primary element B in arange of 0.08%±0.05%; and a fourth primary element W in a range of10%±0.5%.
 18. An alloy comprising four primary elements as follows: afirst primary element Pd as a balance of the alloy; a second primaryelement Ru in a range of 4%±0.5%; a third primary element B in a rangeof 0.08%±0.05%; and a fourth primary element Re in a range of 20%±1%.19. An alloy comprising three primary elements as follows: a firstprimary element Pd as a balance of the alloy; a second primary elementRu in a range of 2%±0.5%; and a third primary element B in a range of0.08%±0.05%.
 20. An alloy comprising: an alloy of palladium andruthenium and a third element, said third element is at least one ofboron, rhenium, iridium, platinum, tungsten, gold, zirconium, cobalt,nickel and tantalum.
 21. A product formed of an alloy, comprising: analloy of palladium and ruthenium and a third element, said third elementis at least one of rhenium, boron, iridium, platinum, tungsten, gold,zirconium, cobalt, nickel and tantalum.
 22. A product as claimed inclaim 21, wherein said product is an in-body medical device.
 23. Aproduct as claimed in claim 21, wherein said product is an electricalcontact.
 24. A product as claimed in claim 23, wherein said electricalcontact is a low noise signal sliding contact.
 25. A product as claimedin claim 23, wherein said electrical contact is a low noise signalstatic contact.
 26. An alloy comprising: an alloy of palladium andrhenium and a third element, said third element is at least one ofboron, ruthenium, iridium, platinum, tungsten, gold, zirconium, cobalt,nickel and tantalum.
 27. A product formed of an alloy, comprising: analloy of palladium and rhenium and a third element, said third elementis at least one of ruthenium, boron, iridium, platinum, tungsten, gold,zirconium, cobalt, nickel and tantalum.
 28. A product as claimed inclaim 27, wherein said product is an in-body medical device.
 29. Aproduct as claimed in claim 27, wherein said product is an electricalcontact.
 30. A product as claimed in claim 29, wherein said electricalcontact is a low noise signal sliding contact.
 31. A product as claimedin claim 29, wherein said electrical contact is a low noise signalstatic contact.